US 4069602 A
Formable or formed stiffening materials, especially for shoe capping, consisting of: at least one backing or layer of fibrous material and at least one thermoplastic synthetic resin, optionally containing fillers, plasticizers, dyes, pigments and/or stabilizers against light, heat and/or mechanical influences, which stiffening materials in a given case have an adhesive coating on one or both sides based on a thermoplastic synthetic resin, containing at least 3 parts of an active substance, e.g., carbon black, in 100 parts of thermoplastic synthetic resins.
1. A method of joining (1) a stiffening material consisting essentially of a fibrous backing or layer having impregnated into said fibrous backing or layer, a thermoplastic synthetic resin stiffening material containing at least three parts per 100 percent of the thermoplastic synthetic resin of an active substance to produce quick and uniform dielectric heating which active substance is finely divided, homogeneously distributed in the stiffening material and is at least one member of the group consisting of carbon black and graphite to (2) an upper material of leather or synthetic resin which is devoid of such active substance without significantly heating the upper material comprising rapidly heating the stiffening material to the temperature at which it becomes soft and adhesive by subjecting the stiffening material and adjacent upper material to an ultra high frequency field.
2. The process of claim 1 wherein the stiffening material has a thermoplastic synthetic resin containing adhesive coating on at least one side thereof.
3. The process of claim 1 wherein the upper material is a shoe capping.
4. The process of claim 1 wherein the fibrous backing or layer is made of leather fibres.
5. The process of claim 1 wherein the active substance is a lamp black.
6. The process of claim 1 wherein the active substance is a furnace black.
7. The process of claim 6 wherein the furnace black has a BET surface area in the range of between 50 and 150 m.sup.2 /g.
8. The process of claim 1 wherein the active substance is a highly structured carbon black.
9. The process of claim 11 wherein the stiffening material contains 10 to 30 parts of active substance per 100 parts of synthetic resin.
10. A method according to claim 1 wherein the stiffening material consists of said fibrous backing impregnated with a composition consisting of said thermoplastic synthetic resin and said active substance.
11. A method according to claim 1, wherein the upper material is shoe or head covering upper material.
12. A method according to claim 11, wherein the active substance is finely divided carbon black homogeneously dispersed through the thermoplastic synthetic resin and the upper material is leather.
13. A method according to claim 12, wherein the active substance is carbon black, the heating is for up to 20 seconds and there are present 3 to 40 parts of carbon black per 100 parts of said thermoplastic synthetic resin.
14. A method according to claim 13, wherein the heating attained is from 65
15. A method according to claim 12, wherein the upper material is shoe upper material for the heel or toe area of the shoe.
16. The product made by the process of claim 14.
17. The product made by the process of claim 13.
18. The product made by the process of claim 12.
19. The product made by the process of claim 11.
20. A method according to claim 11 wherein the active substance is carbon black homogeneously dispersed through the thermoplastic synthetic resin and the upper material is polyvinyl chloride.
21. A method according to claim 20 wherein the heating is for up to 20 seconds and there are present 3 to 40 parts of carbon black per 100 parts of said thermoplastic synthetic resin.
22. A method according to claim 21 wherein the heating attained is from 65
23. A method according to claim 20 wherein the upper material is shoe upper material for the heel or toe area of the shoe.
24. The product made by the process of claim 22.
25. The product made by the process of claim 21.
26. The product made by the process of claim 23.
27. The product made by the process of claim 20.
28. The product made by the process of claim 1.
This is a division, of application Ser. No. 362,056 filed May 21, 1973, now abandoned.
The invention is directed to heat formable or formed stiffening materials which, in addition to at least one backing or layer of fibrous material, also contain at least one thermoplastic synthetic resin as binder or stiffening agent. It serves to stiffen and retain the shape of shaped articles, such as, in particular, shoes and hats, and preferably as toe or heel capping stiffening of shoes. In the shoe industry the stiffening material is often reffered to as capping material.
In the literature there are mentioned numerous types of stiffening materials which contain polymeric binding or stiffening agents. For temporarily softening these materials or to activate their adhesive film, there are used for example, organic solvents, or the softening is attained by heating.
In the pertinent technology, in order to simplify and quicken the processing, increasing preference is being given in the art in question to stiffening materials of the kind whose binders (stiffeners) are suitable to be softened by heat, the structure of the binders being so favourable, or being influenced in such a way, that, after the forming and cooling, the shaped article has attained permanent dimensional stability coupled with a high degree of flexibility. The already preformed stiffening material can be provided on either one or both sides with a layer of a thermoplastic adhesive.
The heat necessary for softening the material or to activate (tackify) the adhesive substance is supplied to the stiffening material, for example, through contact with hot forming surfaces, by steam, by other hot gases, by infrared radiation or the like.
It is further known to use electromagnetic high frequency alternating fields in the range of the so-called microwaves to heat foodstuffs.
It is also known to use microwave absorbers in order to suppress surface wave formation and to reduce the reflection of waves from objects such as antennas and articles used in electronics or in communication transmitters in the high frequency range. As microwave absorbers there have been used, for example, iron powder, carbon powder or ferrite. For this purpose, the microwave absorbers are adhesively applied to the surfaces of these articles, for example, by means of hardening synthetic resins.
It is further known to vulcanize rubber filled with certain carbon blacks or certain silicate fillers in the microwave field. In this way rubber profiles can be produced continuously.
It should be pointed out here that there are important differences between the ultra-high frequency (UHF or microwave field) and the normal high frequency in practical use. Thus, there is no need to adapt the electrodes to the shape of the object, for example, to heat objects of materials with a relatively high or with an adequate loss index (product of the loss factor and the dielectric constant) in the UHF-field, in direct contrast to heating in the usual high frequency field (with lower frequencies). Therefore, one naturally refers to UHF- or microwave-ovens.
Application of the microwave technique known per se to the shoe and related industries was neither obvious nor was it readily possible to employ it without modification specifically to the heating of stiffening materials. In the shoe industry in addition to leather as an upper (shaft) material, synthetic resins, as for example, polyvinyl chloride containing materials, are used in an ever increasing extent. In the microwave heating of the stiffening materials, the upper materials which are adjacent or already partly connected to the stiffening materials should undergo little or no heating because of their heat sensitivity, in other words they should only be heated to an extent that damage to the upper material is excluded. Leather and especially polyvinyl chloride or other known, especially polar, synthetic resins, unfortunately, become heated considerably in the microwave field despite correspondingly adapted residence time in the oven.
Surprisingly, it has now been found that the incorporation of one or more active substances into the stiffening material impregnated or coated with thermoplastic synthetic resins solves the problem. Stiffening material charged in this manner permits the heating with microwaves in a few seconds to the softening or activation temperature of the binding, adhesive or stiffening agent without the other materials connected or bonded to them being heated to any appreciable extent. By virtue of the invention, it is now advantageously possible to use thermoplastic synthetic resins having relatively high softening temperatures for the production of the new stiffening materials whereas, in the past it has not been possible to use thermoplastics of this kind on account of the heat sensitivity of the materials to be stiffened. The use of these thermoplastics with high softening temperatures also imparts considerable advantages in regard to the service properties of the stiffened materials, as for example a better resistance to heat and shape retention, for instance at high summer temperatures.
The formable or formed stiffening materials, especially shoe capping material, according to the invention consists of at least one backing or layer of fibrous material and of at least one thermoplastic synthetic resin as binding or stiffening agent, optionally containing one or more fillers, plasticizers, dyes, pigments and/or stabilizers against light, heat and/or mechanical influences, either individually or in combination. The stiffening material is optionally provided with an adhesive coating based on a thermoplastic synthetic resin on one or both sides (surfaces). The new stiffening material is characterized in that the thermoplastic synthetic resin contains at least one active substance in an amount of at least 3 parts by weight per 100 parts by weight of active substance (or substances) containing synthetic resin. The active substance can be present in an amount of up to 40 parts (or even higher) per 100 parts of active substance containing synthetic resin. The active substance should be present in finely divided, homogeneous distribution in the stiffening material or in the thermoplastic synthetic resin of the stiffening material. The stiffening materials according to the invention are produced preferably in continuous lengths in sheetform, having a thickness from about 1 to a few millimeters; the breadth, depending on the machinery, may vary.
A further object of the invention is the use of the above described stiffening materials as shoe capping material or as cut pieces in a given case in premolded form, especially for stiffening the toe puff (box toe) or, preferably the counter (heel cap) of shoes.
As active substances according to the invention, the most important are carbon blacks. The active substances also include carbon black preparations and carbon black compounds as for example the gray pigments which are produced according to Beschke, British Pat. No. 1,139,620. The entire disclosure of the British patent is hereby incorporated by reference.
For example, there can be used the gray pigment made as described in Example 2 of the Beschke patent by heating 50 parts by weight of lampblack (Flammruss 101) under reflux for 15 minutes at 60 by weight of silicon tetrachloride. The excess silicon tetrachloride is then evaporated off in vacuo. The increase in weight is 2.3 parts by weight.
A suspension of 50 parts by weight of aluminum oxide in 1200 parts by weight of water is heated to 83 The pretreated carbon black is introduced into the suspension over a period of 1 hour, followed by stirring for 30 minutes at 83 then by stirring with the heat off for another three hours. The product is then suction filtered, washed thoroughly with water and dried. 92 parts by weight of gray pigment are obtained.
Similarly there may be used the gray pigments of Examples 1, 3 and 4 of said Beschke patent.
It could not be foreseen that stiffening materials which contain carbon black in sufficient amount, advantageously uniformly distributed in the binder, could be heated in the UHF-field in only a few seconds to the working temperature, without the materials to be stiffened being damaged by the heating. The necessary period of heating time depends f.i. on the quality and the quantity of the active substance being present in the thermoplastic(s); it depends too on the kind of the thermoplastic chosen a.s.o. Generally spoken the heating time can be from about 2 to about 100 seconds, for more practical reasons and preferably from about 5 to 20 seconds. In the context of the invention, the working temperature may be defined as that temperature at which the stiffening material is so plastic or soft that it can be easily formed, shaped or preformed. In the production of shoes the stiffening material is then designated as sufficiently softened for lasting. Carbon black in sufficient amount in this connection means an amount which effects the necessary softness in a few seconds, for example 3, 4 or 6 seconds, or produces easy formability of the stiffening material in the UHF-field. Therefore, the sufficient amount of carbon black which is herein based on the amount of synthetic resin of the binding agent or adhesive is also dependent upon the type or quality of the carbon black.
Although in principle any of the many tested types of carbon black can be used, there exists qualitative differences when it comes to the dielectrical heating of the stiffening materials. Thus, in many cases lamp blacks and furnace blacks are more suitable than gas blacks. These differences relate to the manner of production of the carbon black. In other cases highly structured or as so-called conductive carbon blacks designated types of black are more suitable, which means, that they act more quickly for example in the UHF-field. Additionally, the selection of the thermoplastic synthetic resin plays a role in the dielectric heating of stiffening materials. The more polar the synthetic resin is, the higher is the attained temperature to which the stiffening the material can be heated in the same time, thus for example, the same amount and type of carbon black and amount of stiffening agent based on polyvinyl chloride in the same UHF-field heats in the same time to a higher temperature than when there is employed a stiffening material based on homopolymeric styrene.
However, it had by no means been expected that stiffening materials containing for example 25 parts by weight of furnace blacks with a BET surface area in the range of between 50 and 150 m.sup.2 /g per 100 parts by weight of thermoplastic binding agent (solids contents) would permit to be heated to the working temperature in a conventional UHF-oven of 2.5 KW capacity in 3 seconds, while the material connected thereto or in contact therewith, as for example, leather, remains practically cold.
A further group of active materials are the graphites.
The amount of active substance must be sufficient to produce a quick and highly uniform dielectric heating. The lower limit based on experience is about 3 parts by weight per 100 parts by weight of synthetic resin. The upper limit on the amount introduced into the stiffening materials is not critical for the action in the UHF-field. Larger amounts cause a stronger or quicker effect; lesser amounts a less intense or slower effect, depending on whether reference is made to temperature or time. The upper limits rather are determined by the difficulty encountered in the incorporation of larger amounts; with carbon blacks it dependes on the type of black used, additionally by the "dilution" of the binding, adhesive or stiffening agents by large amounts of the active substance, and/or by too high or too quick heating of the stiffening material. Amounts above about 40 parts by weight per 100 parts of thermoplastic synthetic resin generally do not improve the required effect in an adequate degree but the disadvantages of higher amounts increase, as for example, the decrease of the stiffening effect, the flexibility and the binding effect of the stiffening material. +) see J.Am.Chem.Soc. 60, 309 (1938) According to the type (choice) of active substance the upper limit can be raised considerably if desired, for example, to up to twice or three times the amount of thermoplastic synthetic resin. Preferably the amount of active substance is between 10 and 30 parts by weight for each 100 parts by weight of thermoplastic synthetic resin. In practice, 25 parts by weight are used with advantage, especially in cases where carbon blacks are used. The parts by weight always are based on 100 parts by weight of the thermoplastic synthetic resin which, containing the active substance(s), is used for impregnation and/or for coating the stiffening material (solids content).
The initially flat, film or sheet-like stiffening material is produced in the customary manner in continuous length. As layers or backing of fibrous material preferably there are used textile fiber structures as woven fabrics, nonwoven fabrics, knitted fabrics etc. of natural and/or synthetic fibers, including blended fabrics and including the use of blended yarns or fiber mixtures for the production of the textile structures, preferably of cotton, staple rayon, polyester, e.g., polyethylene terephthalate, polyacrylonitrile, polyamides, e.g. nylon 6, and nylon 6,6, wool, cellulose acetate or propionate, vinyl chloride/vinylidene chloride copolymer, etc. The stiffening material can also be built up from a base fabric and a cover fabric as well as from two or more textile fiber structures. As fibers there can also be used leather fibers or other fiber waste, expecially in preformed heel capping (counters) for shoes.
Thermoplastic synthetic resins are preferred for impregnating or coating the textile fiber structures, for example, there can be used individually or in admixture polystyrene, styrene copolymers, e.g., styrene-butadiene or styrene-acrylonitrile copolymers, especially those with high styrene contents, e.g., at least 60%, styrene acrylate copolymers, e.g., styrene-ethyl acrylate copolymer, styrene-acrylonitrile-butadiene terpolymers, polychlorobutadiene, polyvinyl esters such as polyvinyl acetate, polyacrylates, or polymethacrylates, e.g., polyethyl acrylate, poly 2-ethylhexyl acrylate, polymethyl acrylate, polybutyl methacrylate, polymethyl methacrylate, polyvinyl chloride, after-chlorinated polyvinyl chloride, polyvinylidene chloride, nitrile rubbers (butadiene-acrylonitrile copolymers), ethylene-vinyl acetate co-or terpolymers and ionomeric resins. In a given case, there can be mixed with the thermoplastic synthetic resin in the customary amounts natural resins, e.g. rosin, phenolic resins, e.g., phenolformaldehyde and phenolfurfural, maleic resins, modified colophony resins, ester gums, hydrogenated rosin, rosin modified phenol-formaldehyde or the like known resins. For ground impregnation the aforementioned synthetic resins are generally used in the form of a dispersion. In such case, if desired there can also be employed therewith the already mentioned additives, and, optionally, other conventional additives in customary amounts. If desired, conventional foam producing agents can be additionally used. Very suitable dispersions contain copolymers of styrene and butadiene, copolymers of acrylic acid esters such as butyl acrylate (or ethyl acrylate or octyl acrylate) with monomers such as vinyl chloride, vinylidene chloride, vinyl acetates, vinyl propionate, acrylonitrile, acrylamide and/or acrylic acid. The dispersions are produced in known manner.
The stiffening material can be provided on one or both sides with a so-called adhesive coat based on thermoplastic or heat activatable synthetic resins, for example, based on polychlorobutadiene, polyvinyl acetate, polyacrylic acid esters, e.g., polyethyl acrylate, ethylene-vinyl acetate copolymers or nitrile rubbers (butadiene-acrylonitrile copolymers). If desired and frequently with advantage there can be mixed with the thermoplastic of the adhesive coating other resins, for example, natural resins, phenolic resins, maleic resins, modified rosins or the like resins such as those mentioned above in the customary amounts. These adhesive coatings serve to bond the stiffening material to the substrate to be stiffened. The active substances according to the invention can be worked into these adhesive coatings too or, in some cases, even alone into it. It is also possible, using suitable binders, to incorporate the active substances into intermediate layers between the adhesive coating and the actual stiffening material, additionally or possibly alone.
The fillers which can be mixed into the binders in usual amounts are the solid, powdery materials of natural or synthetic origin known in the related arts. The dyes, pigments, plasticizers and stabilizers belonging to known groups of materials which likewise can be worked in the usual amounts and by known procedures.
Unless otherwise indicated all parts and percentages are by weight.
For the impregnation of fibrous cloth there was used a carbon black synthetic resin dispersion. For this purpose there was first dispersed 20 parts by weight of carbon black in 80 parts by weight of an aqueous solution containing 3.3 weight percent of a wetting agent which was a non-ionic fatty alcohol derivative.
These carbon black dispersions were then stirred into the thermoplastic synthetic resins of various sources, so that 25 or 12.5 parts by weight of carbon black were employed per 100 parts by weight of thermoplastic.
The impregnation of a 300 gram/m.sup.2 heavy cotton fabric napped on both sides was undertaken with the described dispersion in the customary manner so that after the drying of the fabric at about 120 obtained a final weight of about 800 g/m.sup.2.
In Table I there are set forth the various types of carbon black used. Each of these was employed with the synthetic resin dispersion of Example 9 (Table II). In Example 4 there was used a dispersion with 12.5 parts by weight of carbon black; in all the remaining examples there were used 25 parts by weight of carbon black with 100 parts of thermoplastic.
In Examples 9 to 12 (Table II) there were used dispersions of different synthetic resins with the same carbon black, specifically the carbon black of Example 3 in an amount of 25 parts by weight per 100 parts of synthetic resin.
The stiffening materials in Examples 1 to 12 were placed in a microwave oven with a power of 1.2 KW and a frequency of 2450 mc/s. After 3 seconds of residence time in the oven, the originally hard material was soft and optimally formable. Immediately, after taking the material out of the UHF-oven the surface temperature of the stiffening material was measured. The starting temperature of the stiffening materials was room temperature. In the last column of Tables I and II these temperatures are entered. For comparison, a stiffening material which was impregnated with the dispersion according to Example 9 except omitting the carbon black after a residence time of 10 seconds in the microwave oven showed no measurable heating and no softening.
For the use of articles according to the invention which first are produced in sheet form on conventional machines suitable pieces are cut out or punched out and sharpened (i.e., tapered to a pointed edge). These pieces are locally joined to the substrate to be stiffened, in the production of shoes for example with the upper leather, for example, by sewing, or placed in a pocket between the upper materials. Before lasting or before preforming the above identified joined material is introduced into a microwave oven. The stiffening material cut piece is heated in the ultra high frequency field in a few seconds whereby the thermoplastic of the stiffening material is softened and/or the adhesive material found on the surface becomes tacky without the material to be stiffened undergoing any injurious heating. The cut piece can also be heated dielectrically and subsequently formed.
The UHF energy can be supplied for example from a magnetron which operates at the officially permitted frequency of 2450 megacycles.
The stiffening material of the invention preferably serves to stiffen, support and keep in shape toe and heel sections of shoes, for stiffening and keeping in shape head coverings such as hats or caps or parts thereof or bags and trunks.
The upper material of course should be substantially devoid of active substances so that it is not heated when the combination of stock or upper material and stiffening material is subjected to UHF-heating.
TABLE I__________________________________________________________________________ Temper- Average Surface Area ature Particle Size in in m.sup.2 /g in Millimicrons Calcu- after 3 Oil Ab- Arith- lated Accord- seconds Name of Black Type of Black sorption metical Over.sup.2) from ing to in UHF-Ex. Used Used (FP) in % Mean.sup.1) Surface E.M..sup.3) BET oven__________________________________________________________________________1 Flammruss 101 oxidized lamp 280 95 160 19 21 75 black2 Printex A furnace black 300 41 53 63 46 703 Corax 3 HS furnace black of high struc- 430 27 33 94 78 70 ture4 Corax 3 HS furnace black of high struc- 430 27 33 94 78 65 ture5 Printex 30 furnace black 400 27 33 94 78 706 Printex 300 furnace black 360 27 33 94 78 657 Corax L furnace black 560 23 32 93 150 708 SPF 35 furnace black 144.sup.+ -- -- -- 77 70__________________________________________________________________________ .sup.+ DBP (dibutylphthalate) adsorption in ml/100 grams ASTM Iodine adsorption 80.6 mg/g. .sup.1) Measured and calculated from E.M. photographs .sup.2) Calculated from volume divided by surface of the particle (as measured from E.M. photographs). .sup.3) E.M. = Electron Microscope photograph
TABLE II__________________________________________________________________________ Tempera- ture in copolymer Chemical Composition Proportions pH Value Particle 3 Seconds Trade Name of the synthetic in the of the Size in in the UHF-Ex. of the Latex Resin in the Latex Copolymer Latex Microns Oven__________________________________________________________________________9 Pliolite Latex 151 styrene-butadiene 85 : 15 10.3 0.1 - 0.15 70 copolymer -10 Syrofan 2D polystyrene (100) 8-11 0.1 6511 Mowilith D polyvinylacetate (100) 3-5 1-3 10012 Acronal 160 D.sup.+ acrylic acid ester 5-7 -- 105 copolymer__________________________________________________________________________ .sup.+ Acronal 160 D is a 40% plasticizer and solvent free aqueous dispersion of a synthetic resin based on an acrylic acid ester copolymer having a weak anionic character produced by BASF, Ludwigshafen, Germany.